EP1343843B1 - Compositions de polystyrene syndiotactique ayant une plus grande resistance au choc - Google Patents

Compositions de polystyrene syndiotactique ayant une plus grande resistance au choc Download PDF

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EP1343843B1
EP1343843B1 EP00983571A EP00983571A EP1343843B1 EP 1343843 B1 EP1343843 B1 EP 1343843B1 EP 00983571 A EP00983571 A EP 00983571A EP 00983571 A EP00983571 A EP 00983571A EP 1343843 B1 EP1343843 B1 EP 1343843B1
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parts
weight
syndiotactic polystyrene
sps
maleic anhydride
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EP1343843A1 (fr
EP1343843A4 (fr
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Xuequan Zhang
Jae Gon Lim
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Hanwha Total Petrochemicals Co Ltd
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Samsung Atofina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a syndiotactic polystyrene resin composition having good impact strength. More particularly, the present invention relates to a syndiotactic polystyrene resin composition in which a syndiotactic polystyrene-maleic anhydride (sPS-MA) and a hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) are employed as compatibilizers and a diamine compound is added, resulting to provide good impact strength as well as good mechanical properties.
  • sPS-MA syndiotactic polystyrene-maleic anhydride
  • SEBS-MA hydrogenated styrene/butadiene/styrene - maleic anhydride
  • Syndiotactic polystyrene is a very attractive polymer.
  • the polymer shows low specific gravity, low dielectric constant, high flexural modulus, good heat resistance, good rigidity, high melting point (T m ) of about 270°C and excellent resistance to chemicals. Accordingly the syndiotactic polystyrene has become a promising material for various applications in the automotive, electronic and packaging industries. However, the applications of the syndiotactic polystyrene resin composition are highly limited because impact strength is too low.
  • an impact reinforcing material such as rubber and various compatibilizers for the syndiotactic polystyrene and the impact reinforcing material have been used in the syndiotactic polystyrene resin composition.
  • U.S. PatentNo. 5,270,353 to Nakano et al. discloses a styrene-based resin composition comprising a styrene-based polymer having a syndiotactic configuration and no functional group, a styrene-based polymer having an epoxy group and an inorganic filler surface treated by a silane compound or a titanium compound.
  • U.S. Patent No. 5,352,727 to Okada discloses a polystyrene composition comprising syndiotactic polystyrene and a syndiotactic polystyrene impact modifier, said syndiotactic polystyrene impact modifier being the reaction product of a syndiotactic polystyrene having a first reactive functional group, and a rubbery elastomer containing a second reactive functional group, said first and second reactive functional groups being reactive with each other.
  • U.S. Patent No. 5,391,603 to Wessel et al. discloses a composition comprising a syndiotactic, vinylaromatic thermopalstic resin, a rubbery, impact absorbing domain forming polymer, a nucleator for the syndiotactic, vinylaromatic thermoplastic resin, an mineral, glass, ceramic, polymeric or carbon reinforcing agent, and one or more polyarylene ethers or polar group modified polyarylene ethers.
  • U.S. Patent No. 5,543,462 to Okada et al. discloses an impact resistant polystyrene composition comprising a styrenic polymer having syndiotactic configuration and a rubbery elastomer modified by a modifier having a polar group, and optionally a rubbery elastomer and/or a poly(phenylene ether).
  • U.S. Patent No. 5,654,365 to HVeronicaiak, Jr. et al. discloses a syndiotactic polystyrene composition impact-modified by a blend of polystyrene-hydrogenated polybutadiene block copolymers and one or more core/shell modifiers based on a lightly or non-crosslinked rubber core.
  • U.S. Patent No. 5,760,105 to Okada et al. discloses a styrenic resin composition comprising an styrenic polymer having syndiotactic configuration (sPS) or modified sPS, a thermoplastic resin having a polar group, a rubbery elastomer having affinity for the sPS and a compatibilizer having a polar group.
  • sPS syndiotactic configuration
  • a thermoplastic resin having a polar group
  • a rubbery elastomer having affinity for the sPS
  • a compatibilizer having a polar group
  • U.S. Patent No. 5,777,028 to Okada et al. discloses an impact resistant polystyrene composition comprising a styrenic polymer having syndiotactic configuration, a rubbery elastomer having an olefinic component or a polyolefin and a styrene/olefin block or graft copolymer having a microphase separation temperature of 180°C.
  • syndiotactic polystyrene composition There are two major conventional methods to prepare a syndiotactic polystyrene composition. One is to improve elasticity of the syndiotactic polystyrene composition by simply blending a syndiotactic polystyrene and a rubber component, and the other is to improve surface properties between a syndiotactic polystyrene and a rubber component by using another rubber component as a compatibilizer to prevent phase separation at the surface.
  • the latter method is more preferable in processability and physical properties.
  • the latter method focuses on improvement of polarity of both the syndiotactic polystyrene and the rubber component but does not contribute improvement of impact strength to the syndiotactic polystyrene composition.
  • the present inventors have developed a syndiotactic polystyrene resin composition with good impact strength as well as good mechanical properties, in which a syndiotactic polystyrene - maleic anhydride (sPS-MA) and a hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) are employed as compatibilizers and a diamine compound is added as a coupling agent.
  • the compatibilizers and coupling agent improve polarity of both the syndiotactic polystyrene and the rubber component and impact strength of the syndiotactic polystyrene composition.
  • a feature of the present invention is the provision of a syndiotactic polystyrene resin composition with good impact strength as well as good mechanical properties.
  • Another feature of the present invention is the provision of a syndiotactic polystyrene resin composition with good compatibility between a syndiotactic polystyrene and a rubber component, in which a syndiotactic polystyrene - maleic anhydride (sPS-MA) and a hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) are employed as compatibilizers and a diamine is added as a coupling agent
  • sPS-MA syndiotactic polystyrene - maleic anhydride
  • SEBS-MA hydrogenated styrene/butadiene/styrene - maleic anhydride
  • a further feature of the present invention is the provision of a syndiotactic polystyrene resin composition having good physical properties that are required for various applications thereof.
  • the syndiotactic polystyrene resin composition according to the present invention is superior in compatibility between a syndiotactic polystyrene and a rubber component and mechanical properties such as impact strength, in which a syndiotactic polystyrene - maleic anhydride (sPS-MA) and a hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) are employed as compatibilizers and a diamine compound is added as a coupling agent.
  • sPS-MA syndiotactic polystyrene - maleic anhydride
  • SEBS-MA hydrogenated styrene/butadiene/styrene - maleic anhydride
  • the compatibilizers and coupling agents improve the polarity between the syndiotactic polystyrene of the main matrix part and SEBS of the rubber domain part, and the impact strength of the syndio
  • the syndiotactic polystyrene resin composition according to the present invention has good compatibility between a syndiotactic polystyrene and a rubber component and good mechanical properties such as impact strength.
  • the syndiotactic polystyrene composition employs a syndiotactic polystyrene - maleic anhydride (sPS-MA) and a hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) as compatibilizers and a diamine compound as a coupling agent.
  • the compatibilizers and coupling agent may improve polarity of both the syndiotactic polystyrene and the rubber component and impact strength of the syndiotactic polystyrene composition.
  • the hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) and the syndiotactic polystyrene - maleic anhydride (sPS-MA) carry out a coupling reaction with a diamine compound to improve uniform mixing of the syndiotactic polystyrene and the rubber component.
  • the coupling reaction between the hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) and the syndiotactic polystyrene - maleic anhydride (sPS-MA) is represented as follow: where R is
  • polystrenes are classified into an atactic, an isotactic and a syndiotactic structure depending on the position of benzene rings as side chains.
  • An atactic polystyrene has an irregular arrangement of the benzene rings and an isotactic polystyrene has an arrangement that the benzene rings are positioned at one side of the polymer main chain.
  • a syndiotactic polystyrene has a regularly alternating arrangement of the benzene rings.
  • the syndiotactic polystyrenes are prepared with styrene monomers under the catalyst system of a metallocene catalyst and a cocatalyst.
  • the metallocene catalyst has a bridged structure of a complex of Group IV transition metals such as Ti, Zr, Hf etc. in the Periodic Table and a ligand having one or two cycloalkane dienyl groups such as cyclopentadienyl group, indenyl group, fluorenyl group, and derivatives thereof.
  • the catalysts can prepare polymers having better physical properties than the Ziegler-Natta catalysts.
  • 08/844,109 and 08/844,110 disclose new alkyl-bridged binuclear metallocene catalysts, silyl-bridged binuclear metallocene catalysts, and alkyl-silyl-bridged binuclear metallocene catalysts to polymerize styrenes to produce polystyrene having high stereoregularity, high melting point, and good molecular weight distribution.
  • syndiotactic polystyrene with a syndiotacticity of 97 % or more in this invention.
  • the syndiotactic polystyrene is used in the amount of about 50 ⁇ 95 parts by weight per 100 parts of the resin composition.
  • a rubber component is added to the syndiotactic polystyrene resin composition according to the present invention.
  • a hydrogenated styrene/butadiene/styrene block copolymer (SEBS) is preferably used as a rubber component.
  • SEBS hydrogenated styrene/butadiene/styrene block copolymer
  • PP polypropylene rubber
  • EPDM ethylene/propylene/diene rubber
  • EVA ethyl vinyl acetate
  • the rubber component absorbs impact and improves impact strength of the resin composition.
  • the runner component is used in the amount of about 1 ⁇ 95 parts by weight per 100 parts of the resin composition.
  • SEBS hydrogenated styrene/butadiene/styrene - maleic anhydride
  • SEBS-MA hydrogenated styrene/butadiene/styrene - maleic anhydride
  • the hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) is prepared by treating hydrogenated styrene/butadiene/styrene with maleic anhydride, which can be carried out by an ordinary skilled person in the art. Also, the hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) is commercially available.
  • a polypropylene - graft- maleic anhydride (PP-g-MA) is used as a first compatibilizer to improve compatibility between the syndiotactic polystyrene and the rubber component.
  • the polypropylene - graft - maleic anhydride (PP-g-MA) is prepared by treating polypropylene with maleic anhydride, which can be carried out by an ordinary skilled person in the art. Also, the polypropylene - graft - maleic anhydride (PP-g-MA) is commercially available.
  • EPDM ethylene/propylene/diene - graft - maleic anhydride
  • EPDM-g-PS ethylene/propylene/diene - graft - polystyrene
  • the ethylene/propylene/diene - graft - maleic anhydride (EPDM-g-MA) is prepared by grafting maleic anhydride onto ethylene/propylene/diene, which can be carried out by an ordinary skilled person in the art. Also, the EPDM-g-MA is commercially available.
  • the ethylene/propylene/diene - graft - polystyrene (EPDM-g-PS) is prepared by polystyrene onto ethylene/propylene/diene, which can be carried out by an ordinary skilled person in the art. Also, the EPDM-g-PS is commercially available.
  • diamine may not be used.
  • the first compatibilizer is used in the amount of about 0 ⁇ 20 parts by weight per 100 parts of the resin composition.
  • a syndiotactic polystyrene - maleic anhydride (sPS-MA) is used in the syndiotactic polystyrene resin composition according to the present invention as a second compatibilizer to improve compatibility between the syndiotactic polystyrene and the rubber component.
  • syndiotactic polystyrene - maleic anhydride (sPS-MA) is prepared by treating syndiotactic polystyrene with maleic anhydride, which can be carried out by a special method. So, the syndiotactic polystyrene - maleic anhydride (sPS-MA) is not commercially available.
  • the second compatibilizer is used in the amount of about 0 ⁇ 10 parts by weight per 100 parts of the resin composition.
  • PPO is added to the syndiotactic polystyrene resin composition according to the present invention to improve compatibility between the syndiotactic polystyrene and the rubber component.
  • PPO is commercially available.
  • Polyphenyleneoxide (PPO) is used in the amount of about 0 ⁇ 10 parts by weight per 100 parts of the resin composition.
  • the hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA) and the syndiotactic polystyrene - maleic anhydride (sPS-MA) carry out a coupling reaction with a coupling agent to improve uniform mixing of the syndiotactic polystyrene and the rubber component.
  • the coupling agent is preferably a diamine compound.
  • Diamine compound is used in the amount of about 0.02 ⁇ 20 parts by weight per 100 parts of the resin composition.
  • the syndiotactic polystyrene resin composition according to the present invention may optionally include a reinforcing material.
  • a reinforcing material may be added to the syndiotactic polystyrene resin composition according to the present invention.
  • Glass fibers may be preferably used as a reinforcing material in this invention.
  • Glass fibers are used in the amount of about 5 ⁇ 40 parts by weight per 100 parts of the resin composition.
  • additives may be added to the resin composition of the present invention, if necessary.
  • the additives include an additional flame retardant, a lubricant, a releasing agent, an anti-dripping agent, an impact modifier, a plasticizer, a heat stabilizer, an anti-oxidant , a light stabilizer, pigments, dye and the like.
  • An inorganic filler such as talc, silica, mica or ceramic can be added too.
  • the additives are employed in an amount of about 0 to 40 parts by weight as per 100 parts of the resin composition.
  • a first syndiotactic polystyrene resin composition according to the present invention comprises about 50 ⁇ 95 parts by weight of syndiotactic polystyrene (sPS), about 2 ⁇ 20 parts by weight of hydrogenated styrene/butadiene/styrene block copolymer (SEBS), about 1 ⁇ 10 parts by weight of hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA), about 1 ⁇ 10 parts by weight of syndiotactic polystyrene - maleic anhydride (sPS-MA), about 1 ⁇ 10 parts by weight of polyphenyleneoxide (PPO), about 0.02 ⁇ 20 parts by weight of diamine, and optionally about 5 ⁇ 30 parts by weight of glass fibers.
  • sPS syndiotactic polystyrene
  • SEBS hydrogenated styrene/butadiene/styrene block copo
  • a second syndiotactic polystyrene resin composition comprises about 50 ⁇ 96 parts by weight of syndiotactic polystyrene (sPS), about 1 ⁇ 20 parts by weight of polypropylene rubber (PP), about 1 ⁇ 10 parts by weight of polypropylene - graft - maleic anhydride (PP-g-MA), about 1 ⁇ 10 parts by weight of syndiotactic polystyrene - maleic anhydride (sPS-MA), about 1 ⁇ 10 parts by weight of polyphenyleneoxide (PPO), and about 0.02 ⁇ 30 parts by weight of diamine.
  • sPS syndiotactic polystyrene
  • PP polypropylene rubber
  • PP-g-MA polypropylene -g-MA
  • sPS-MA syndiotactic polystyrene -maleic anhydride
  • PPO polyphenyleneoxide
  • a third syndiotactic polystyrene resin composition comprises about 50 ⁇ 96 parts by weight of syndiotactic polystyrene (sPS), about 1 ⁇ 20 parts by weight of ethylene/propylene/diene rubber (EPDM), about 1 ⁇ 10 parts by weight of ethylene/propylene/diene - graft - maleic anhydride (EPDM-g-MA) or ethylene/propylene/diene - graft - polystyrene (EPDM-g-PS), about 1 ⁇ 10 parts by weight of syndiotactic polystyrene - maleic anhydride (sPS-MA), about 1 ⁇ 10 parts by weight of polyphenyleneoxide (PPO), and about 0.02 ⁇ 30 parts by weight of a diamine.
  • sPS syndiotactic polystyrene
  • EPDM ethylene/propylene/diene rubber
  • EPDM-g-MA ethylene/propylene/
  • a fourth syndiotactic polystyrene resin composition according to the present invention comprises about 2 ⁇ 90 parts by weight of syndiotactic polystyrene (sPS), about 0 ⁇ 10 parts by weight of hydrogenated styrene/butadiene/styrene block copolymer (SEBS), about 2 ⁇ 10 parts by weight of hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA), about 0 ⁇ 10 parts by weight of syndiotactic polystyrene - maleic anhydride (sPS-MA), about 2 ⁇ 10 parts by weight of polyphenyleneoxide (PPO), about 0.02 ⁇ 20 parts by weight of diamine, and about 6 ⁇ 90 parts by weight of ethyl vinyl acetate copolymer (EVA).
  • sPS syndiotactic polystyrene
  • SEBS hydrogenated styrene/
  • a fifth syndiotactic polystyrene resin composition according to the present invention comprises about 2 ⁇ 93 parts by weight of syndiotactic polystyrene (sPS), about 0 ⁇ 10 parts by weight of hydrogenated styrene/butadiene/styrene block copolymer (SEBS), about 1 ⁇ 10 parts by weight of syndiotactic polystyrene - maleic anhydride (sPS-MA), about 1 ⁇ 10 parts by weight of polyphenyleneoxide (PPO), about 5 ⁇ 90 parts by weight of ethyl vinyl acetate copolymer (EVA), and about 1 ⁇ 50 parts by weight of glass fibers.
  • sPS syndiotactic polystyrene
  • SEBS hydrogenated styrene/butadiene/styrene block copolymer
  • sPS-MA syndiotactic polystyrene - maleic anhydr
  • the syndiotactic polystyrene resin compositions according to the present invention are prepared from (A) a syndiotactic polystyrene (sPS), (B) a rubber component of SEBS, PP, EPDM and EVA, (C) a first compatibilizer of hydrogenated styrene/butadiene/styrene - maleic anhydride (SEBS-MA), polypropylene - graft - maleic anhydride (PP-g-MA), ethylene/propylene/diene - graft - maleic anhydride (EPDM-g-MA) and ethylene/propylene/diene - graft - polystyrene (EPDM-g-PS), (D) a second compatibilizer of syndiotactic polystyrene - maleic anhydride (sPS-MA), (E) polyphenyleneoxide (PPO), (F) a coupling agent of a diamine compound,
  • Syndiotactic polystyrene with syndiotacticity of 97 % was prepared in a glass reactor.
  • Styrene monomers were polymerized in a glass reactor equipped with a temperature controller, a magnetic agitator or a mechanical agitator, and valves through which the monomers and nitrogen were fed.
  • methyl aluminoxane as a cocatalyst added and the reactor was agitated for 30 minutes. Sufficient amount of catalyst was added to the reactor.
  • Polymerization was initiated at 70 °C. After reaction for one hour, the polymerization was terminated by adding methanol. The resulting solution was washed with methanol in excess and sodium hydroxide and filtered. The resulting polymer was dried at 90 °C in vacuum for about 4 hours to obtain syndiotactic polystyrene.
  • syndiotactic polystyrene prepared above was reacted with dicumylperoxide and maleic anhydride in a 10 L reactor to produce syndiotactic polystyrene - maleic anhydride (sPS-MA) as a second compatibilizer.
  • sPS-MA syndiotactic polystyrene - maleic anhydride
  • P401 A commercial product (P401) of Asahi Co. of Japan was used as PPO.
  • Example 1 The components of Example 1 and Comparative Examples 1-4 are shown in Table 1.
  • Example 1 and Comparative Examples 1-4 were prepared in a batch type mixer of Haake Co. of Germany by mixing at 50 rpm and 280 °C for seven minutes. Specimens of 1/8" were prepared at 300 °C in a mold according to ASTM D256 and Izod impact strength were measured therefore in accordance with ASTM D638. The Izod impact strengths are shown in Table 1. The resin composition of Example 1 using sPS-MA and diamine shows better Izod impact strength than the resin compositions of Comparative Examples 1-4.
  • the resin compositions of Example 1 and Comparative Example 2 were prepared in pellets in a twin screw extruder at 280°C. The pellets were dried at 80°C for 3 hours and molded into specimens in a 50ton injection molding machine at 300°C.
  • the Comparative Example 2 was to prepare a resin composition according to U.S. Patent No. 5,777,028. The physical properties such as yield strength, breaking strength, elongation, flexural rigidity and flexural strength. The physical properties are shown in Table 2.
  • Example 1 Comparative Example 2 yield strength (kgf/cm 2 ) 439 434 breaking strength (kgf/cm 2 ) 427 384 elongation (%) 4 - 4 flexural rigidity (kgf/cm 2 ) 711 705 flexural strength (kgf/cm 2 ) 24,410 24,040 Notes: The yield strength and breaking strength were measured in accordance with ASTM D638 and the elongation, flexural rigidity and flexural strength were measured in accordance with ASTM D790.
  • Example 2 As shown in Table 2, the resin composition of Example 1 using sPS-MA and diamine shows better yield strength, breaking strength, flexural rigidity and flexural strength than the resin composition of Comparative Example 2.
  • Examples 2-8 were conducted in the same manner as in Example 1 except the components of Table 3.
  • the Izod impact strengths are shown in Table 3.
  • Examples 2 3 4 5 6 7 8 (A) sPS 57 67 63 65 56 58 57 (B) (B 1 ) SEBS 12 12 12 12 3 4 3 (C) (C 1 ) SEBS-MA 3 3 3 3 0 0 0 (C 3 ) (EPDM-g-PS) 0 0 0 0 12 19 12 (D) sPS-MA 12 3 6 4 3 3 3 (E) PPO 3 3 3 3 3 3 3 (F) Diamine 1 0 1 1 1 1 0 (G) Glass Fibers 15 15 15 15 15 25 15 25 Izod Impact Strength (kgf.cm/cm) 3.5 3.8 4.2 10.7 2.8 3.3 2.6
  • Examples 9-17 and Comparative Example 5 are shown in Table 4.
  • Examples 9-17 and Comparative Example 5 were conducted in the same manner as in Example 1 except the components of Table 4.
  • the Izod impact strengths are shown in Table 4.
  • Figure 1 is a scanning electron microscope (SEM) photograph of the surface of syndiotactic polystyrene/polypropylene of Comparative Example 5
  • Figure 2 is a scanning electron microscope (SEM) photograph of the surface of sPS/sPS-MA/PP/PP-MA//diamine(76/4/16/4/2). As shown in Figure 1, the surface is not uniform and the Izod impact strength is poor.
  • Examples 18-19 and Comparative Examples 6-12 are shown in Table 5. Examples 18-19 and Comparative Examples 6-12 were conducted in the same manner as in Example 1 except the components of Table 5. The Izod impact strengths are shown in Table 5. Examples Comparative Examples 18 19 6 7 8 9 10 11 12 (A) sPS 72 72 72 80 80 76 76 76 (B) (B 1 ) SEBS 4 0 4 0 0 4 4 0 0 (B 3 ) EPDM 0 0 16 20 0 16 0 20 0 (C) (C 4 ) EPDM-g-MA 16 20 0 0 20 0 16 0 20 (D) sPS-MA 4 4 4 0 0 0 0 0 0 (L) PPO 4 4 4 0 0 4 4 4 (F) Diamine 1 1 1 0 0 0 0 0 0 0 0 Izod Impact Strength (kgf.cm/cm) 8.25 8.93 2.78 2.88 2.97 6.21 2.60 5.44 3.25
  • Examples 20-27 are shown in Table 6. Examples 20-27 were conducted in the same manner as in Example 1 except the components of Table 6. The Izod impact strengths are shown in Table 6. Examples 20 21 22 23 24 25 26 27 (A) sPS 82 72 62 42 32 22 12 2 (B) (B 4 ) EVA 6 16 26 46 56 66 76 86 (C) (C 1 ) SEBS-MA 4 4 4 4 4 4 4 (D) sPS-MA 4 4 4 4 4 4 4 (E) PPO 4 4 4 4 4 4 4 4 (F) Diamine 1 1 1 1 1 1 1 1 1 1 Izod Impact Strength (kgf.cm/cm) 6.75 4.33 3.33 9.66 10.65 16.95 non-brake - non-brake 10.91 non-brake
  • sPS may preferably be used in about 35 ⁇ 40 parts by weight and EVA may preferably be used in about 55 ⁇ 60 parts by weight.
  • Examples 28-35 are shown in Table 7. Examples 28-35 were conducted in the same manner as in Example 1 except the components of Table 7. The Izod impact strengths are shown in Table 7. Examples 28 29 30 31 32 33 34 35 (A) sPS 32 33 36 32 36 36 40 0 (B) (B 1 ) SEBS 4 4 4 4 0 0 0 0 (B 4 ) EVA 56 55 56 60 56 60 60 100 (D) sPS-MA 4 4 0 4 4 4 0 0 (E) PPO 4 4 4 0 4 0 0 0 (G) Glass Fibers 15 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 I
  • the resin composition (Example 35) consisting of EVA and GF shows a poor impact strength compared to other resin compositions.
  • Eva is rubber component for absorbing impact and can be used more economically than SEBS.

Abstract

Cette invention se rapporte à une composition de résine de polystyrène syndiotactique, qui offre une plus grande compatibilité entre un polystyrène syndiotactique et un composant de caoutchouc, ainsi que des propriétés mécaniques supérieures, par exemple la résistance au choc. Dans cette composition, un composé polystyrène syndiotactique-anhydride maléique (sPS-MA) et un composé styrène/butadiène/styrène hydrogéné-anhydride maléique (SEBS-MA) sont utilisés comme agents de compatibilisation et un composé diamine est ajouté pour servir d'agent de couplage. Les agents de compatibilisation et les agents de couplage améliorent la polarité à la fois du polystyrène syndiotactique et du composant de caoutchouc, ainsi que la résistance au choc de la composition de polystyrène syndiotactique.

Claims (8)

  1. Composition de résine polystyrène syndiotactique comprenant (a) environ 50 - 95 parties en poids de polystyrène syndiotactique (sPS), (b) environ 2 - 20 parties en poids de copolymère bloc styrène hydrogéné/butadiène/styrène (SEBS), (c) environ 1 - 10 parties en poids de styrène hydrogéné/butadiène/styrène - anhydride maléique (SEBS-MA), (d) environ 1 - 10 parties en poids de polystyrène syndiotactique - anhydride maléique (sPS-MA), (e) environ 1 - 10 parties en poids d'oxyde de polyphénylène (PPO) et (f) environ 0,02 - 20 parties en poids de diamine.
  2. Composition de résine polystyrène syndiotactique selon la revendication 1, comprenant également (g) environ 5 - 30 parties en poids de fibres de verre.
  3. Composition de résine polystyrène syndiotactique comprenant (a) environ 50 - 96 parties en poids de polystyrène syndiotactique (sPS), (b) environ 1 - 20 parties en poids de caoutchouc de polypropylène (PP), (c) environ 1 - 10 parties en poids de polypropylène - greffe - anhydride maléique (PP-g-MA), (d) environ 1 - 10 parties en poids de polystyrène syndiotactique - anhydride maléique (sPS-MA), (e) environ 1 - 10 parties en poids d'oxyde de polyphénylène (PPO) et (f) environ 0,02 - 30 parties en poids de diamine.
  4. Composition de résine polystyrène syndiotactique comprenant (a) environ 50 - 96 parties en poids de polystyrène syndiotactique (sPS), (b) environ 1 - 20 parties en poids de caoutchouc éthylène/propylène/diène (EPDM), environ 1 - 10 parties en poids de éthylène/propylène/diène - greffe - anhydride maléique (EPDM-g-MA) ou de éthylène/propylène/diène - greffe - polystyrène (EPDM-g-PS), (d) environ 1 - 10 parties en poids de polystyrène syndiotactique - anhydride maléique (sPS-MA), (e) environ 1 - 10 parties en poids d'oxyde de polyphénylène (PPO), et (f) environ 0,02 - 30 parties en poids de diamine.
  5. Composition de résine polystyrène syndiotactique selon l'une quelconque des revendications 1-4, comprenant également un ignifuge supplémentaire, un lubrifiant, un agent de démoulage, un agent anti-égouttement, un modificateur de choc, un plastifiant, un stabilisant thermique, un antioxydant, un stabilisant de lumière, des pigments, de la teinture et/ou une charge inorganique.
  6. Composition de résine polystyrène syndiotactique comprenant (a) environ 2 - 93 parties en poids de polystyrène syndiotactique (sPS), (b) environ 0 - 10 parties en poids de copolymère bloc styrène hydrogéné/butadiène/styrène (SEBS), (c) environ 1 - 10 parties en poids de polystyrène syndiotactique - anhydride maléique (sPS-MA), (d) environ 1 - 10 parties en poids d'oxyde de polyphénylène (PPO) et (e) environ 5 - 90 parties en poids de copolymère d'acétate éthylvinylique (EVA), et (f) environ 1 - 50 parties en poids de fibres de verre.
  7. Composition de résine polystyrène syndiotactique comprenant (a) environ 2 - 90 parties en poids de polystyrène syndiotactique (sPS), (b) environ 0 - 10 parties en poids de copolymère bloc styrène hydrogéné/butadiène/styrène (SEBS), (c) environ 2 - 10 parties en poids de styrène hydrogéné/butadiène/styrène - anhydride maléique (SEBS-MA), (d) environ 0 - 10 parties en poids de polystyrène syndiotactique - anhydride maléique (sPS-MA), (e) environ 2 - 10 parties en poids d'oxyde de polyphénylène (PPO) et (f) environ 0,02 - 20 parties en poids de diamine, et (g) environ 50 - 95 parties en poids de copolymère d'acétate éthylvinylique (EVA).
  8. Composition de résine polystyrène syndiotactique selon la revendication 6 ou 7, comprenant également un ignifuge supplémentaire, un lubrifiant, un agent de démoulage, un agent anti-égouttement, un modificateur de choc, un plastifiant, un stabilisant thermique, un antioxydant, un stabilisant de lumière, des pigments, de la teinture et/ou une charge inorganique.
EP00983571A 2000-12-18 2000-12-18 Compositions de polystyrene syndiotactique ayant une plus grande resistance au choc Expired - Lifetime EP1343843B1 (fr)

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CN1326899C (zh) * 2004-09-14 2007-07-18 中国石化集团巴陵石油化工有限责任公司 一种极性化的sebs及其制备方法
WO2007010787A1 (fr) * 2005-07-15 2007-01-25 Sanc Salaam Corporation Composition de polymère thermoplastique à libération prolongée et produit comprenant celle-ci
US20070224908A1 (en) * 2006-03-24 2007-09-27 Graydon Vaught Gas assisted game call
US8846802B2 (en) * 2006-06-06 2014-09-30 Sabic Innovative Plastics Ip B.V. Thermoplastic elastomer composition, method of making and articles thereof
US7718721B2 (en) * 2006-11-13 2010-05-18 Sabic Innovative Plastics Ip B.V. Poly(arylene ether)/polyolefin composition, method, and article
CN101851372A (zh) * 2010-05-28 2010-10-06 广东盛恒昌化学工业有限公司 高温热氧稳定的浅色柔性聚苯醚/聚丙烯树脂组合物
CN102321358A (zh) * 2010-12-02 2012-01-18 北京首塑新材料科技有限公司 一种耐高温易涂装ppo合金及其制备方法
US8686079B2 (en) * 2012-04-13 2014-04-01 Sabic Innovative Plastics Ip B.V. Compatibilized composition, method for the formation thereof, and article comprising same
WO2014197834A1 (fr) 2013-06-06 2014-12-11 Halliburton Energy Services, Inc. Traitement de puits pour perte de fluide
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EP1343843A1 (fr) 2003-09-17
US20040030014A1 (en) 2004-02-12
EP1343843A4 (fr) 2004-04-28
DE60015403D1 (de) 2004-12-02
CN1461331A (zh) 2003-12-10
CN1219818C (zh) 2005-09-21
DE60015403T2 (de) 2005-03-24
WO2002050182A1 (fr) 2002-06-27
JP2004516353A (ja) 2004-06-03
US6875804B2 (en) 2005-04-05
AU2001220309A1 (en) 2002-07-01

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